TWI660526B - Light-emitting element, light-emitting device, and manufacturing method thereof - Google Patents

Abstract

Provide light-emitting element capable of improving heat resistance and miniaturization Pieces, light-emitting devices, and their manufacturing methods.

A plurality of LEDs are mounted on the substrate 11 The semiconductor light emitting wafer 12 has a wavelength conversion member 14 disposed on the semiconductor light emitting wafer 12 in contact with the semiconductor light emitting wafer 12. The wavelength conversion member 14 is formed by coating a phosphor film material on one side of the substrate 14A and reacting it at normal temperature or heat-treating at a temperature of 500 ° C or lower. The phosphor film material includes a phosphor. A material and an adhesive material including at least one selected from the group consisting of a silicon oxide precursor, a silicic acid compound, silica, and an amorphous silica, which become silicon oxide by hydrolysis or oxidation.

Description

Light-emitting element, light-emitting device, and manufacturing method thereof

The present invention relates to a light-emitting element using a phosphor material, a light-emitting device, and a method for manufacturing the same.

As a light-emitting device using a phosphor, for example, it is known to disperse the phosphor in an epoxy resin or a silicone resin and arrange it (for example, refer to Patent Document 1 or Patent Document 2). However, in this light-emitting device, as the output of the LED is increased or the heat of the LED is generated, the epoxy resin or the silicone resin is deteriorated, deformed, or peeled off, and there is a problem that it is difficult to achieve high output. As a countermeasure against this, for example, a light-emitting device in which a phosphor is dispersed in a glass instead of an epoxy resin or a silicone resin has been developed (for example, refer to Patent Documents 3 to 5). According to this light-emitting device, the heat resistance of the structure can be improved by using an inorganic material in the dispersion medium.

[Prior technical literature] [Patent Literature]

[Patent Document 1] Japanese Patent No. 3364229

[Patent Document 2] Japanese Patent No. 3824917

[Patent Document 3] Japanese Patent Laid-Open No. 2009-91546

[Patent Document 4] Japanese Patent Laid-Open No. 2008-143978

[Patent Document 5] Japanese Patent Laid-Open No. 2008-115223

However, it is difficult to soften a general low-melting glass to such an extent that it can disperse the phosphor without heating it to substantially 500 ° C. or higher (refer to Example of Reference 4). For example, it is possible to lower the melting point by adding heavy metals such as lead, but from the standpoint of the impact on the environment or the human body, the use of those elements is currently rare. Therefore, there is a problem that the performance of the phosphor is deteriorated due to the influence of heat.

In addition, when the phosphor is dispersed in glass, in order to maintain the strength of the glass used as the base material, the fill rate of the phosphor cannot be increased. With the high brightness of the LED, more than necessary excitation light is transmitted. problem. In order to suppress this transmission, it is necessary to increase the thickness of the glass in which the phosphor has been dispersed. As a result, it is not possible to reduce the thickness of the light-emitting device, and the light transmittance is decreased due to an increase in the thickness of the glass, and there are problems such as hindering heat generation.

The present invention has been made based on such a problem, and an object thereof is to provide a light-emitting element, a light-emitting device, and a method for manufacturing the same that can improve heat resistance and can be miniaturized.

The light-emitting device according to claim 1 includes a semiconductor light-emitting wafer and a wavelength conversion member disposed in contact with the semiconductor light-emitting wafer; the wavelength conversion member includes a substrate and a phosphor film; and the phosphor film is formed here. At least one side of the substrate contains particulate phosphor material and a binder; the phosphor film is formed by coating the phosphor film material on at least one side of the substrate to make it react at normal temperature or at 500 ℃ Formed by heat treatment at the following temperature, the phosphor film raw material includes a phosphor material and a binder raw material, and the binder raw material includes a silicon oxide precursor including a silicon oxide by hydrolysis or oxidation, a silicic acid compound, At least one of the group of silica and amorphous silica.

The method for manufacturing a light-emitting device according to claim 7 is a method for manufacturing a light-emitting device including a semiconductor light-emitting wafer and a wavelength conversion member disposed in contact with the semiconductor light-emitting wafer. The wavelength conversion member includes a substrate and a phosphor. The phosphor film is formed on at least one side of the substrate, and includes a particulate phosphor material and an adhesive. The phosphor film is coated on at least one side of the substrate by a printing method. The body film material is formed by reacting it at normal temperature or heat treatment at a temperature below 500 ° C. The material of the phosphor film includes a phosphor material and a binder material, and the binder material includes At least one of a group of silicon oxide precursors, silicic acid compounds, silica, and amorphous silica that becomes silicon oxide.

The light-emitting element according to claim 8 is one in which a wavelength conversion member is disposed on a semiconductor light-emitting wafer using an adhesive. The wavelength conversion member has a substrate and a phosphor film formed on the substrate. At least one side contains a particulate phosphor material and an adhesive: a phosphor film is formed by coating a phosphor film raw material on at least one side of a substrate to be reacted at normal temperature or at a temperature of 500 ° C or lower It is formed by heat treatment. The phosphor film material includes a phosphor material and a binder material. The binder material includes a silicon oxide precursor, a silicic acid compound, silica, and a non-silicon oxide. At least one of the group of crystalline silica; the adhesive is made by reacting the adhesive raw material at normal temperature Or obtained by heat treatment at a temperature of 500 ° C or lower, the raw material of the adhesive includes silicon oxide precursors that become silicon oxide by hydrolysis or oxidation, silicic acid compounds, phosphoric acid compounds, and at least a part of carbon is detached by heating At least one of the groups of inorganic-bonded silicone resins.

The light-emitting device according to claim 14 includes a light-emitting element according to claim 8.

The method for manufacturing a light-emitting element according to claim 15 is a method of manufacturing a light-emitting element in which a wavelength conversion member is disposed on a semiconductor light-emitting wafer using an adhesive, and the wavelength conversion member has at least a substrate and a substrate formed thereon. One side of the phosphor film, the phosphor film contains a particulate phosphor material and an adhesive; the phosphor film is coated with a phosphor film material on at least one side of a substrate by a printing method, and It is formed by reaction at normal temperature or heat treatment at a temperature below 500 ° C. The phosphor film raw material includes a phosphor material and a binder raw material, and the binder raw material includes a silicon oxide precursor including silicon oxide which becomes silicon oxide by hydrolysis or oxidation. At least one of the group consisting of an organic substance, a silicic acid compound, silica, and amorphous silica. The semiconductor light emitting chip and the wavelength conversion member are connected by an adhesive, and the adhesive is made by making the adhesive raw material at room temperature. It can be obtained by the next reaction or heat treatment at a temperature below 500 ° C. The raw material of the adhesive includes a silicon oxide precursor that is converted into silicon oxide by hydrolysis or oxidation, and silicified. Thereof, phosphoric acid compounds, and by heating at least a portion of at least one carbon to become disengaged inorganic group bonded to silicon resin.

The light-emitting device according to claim 1 is a method of using a binder composed mainly of an inorganic material depending on the wavelength conversion member. Since the formula is performed, heat resistance to heat generated from the semiconductor light emitting wafer can be improved, and high output and high brightness can be achieved. In addition, since the wavelength conversion member is formed by coating the phosphor film material on at least one side of the substrate, the filling rate of the phosphor material in the phosphor film can be increased, and the phosphor can be thinned. The thickness of the film, wherein the phosphor film raw material includes a phosphor material and a binder raw material, the binder raw material includes a silicon oxide precursor, a silicic acid compound, silica, and At least one of the group of amorphous silica. As a result, it is possible to reduce the size, improve the heat radiation efficiency, and increase the degree of freedom in design. In addition, since the phosphor film is obtained by reaction at normal temperature or heat treatment at a temperature of 500 ° C. or lower, it can be formed at a low temperature, and the deterioration of the characteristics of the phosphor material can be suppressed.

In addition, if the average particle diameter of the primary particles of the phosphor material is set to 1 μm or more and 20 μm or less, or if the film thickness distribution of the phosphor film is set to within ± 10%, Alternatively, if the surface roughness of the phosphor film is set to an arithmetic mean roughness Ra of 10 μm or less, color unevenness can be suppressed, uniformity can be achieved, and performance can be stabilized. In addition, if the thickness of the substrate to be formed is set to 0.05 mm or more and 3 mm or less, the shape can be maintained and the size can be reduced.

The method for manufacturing a light-emitting device according to claim 7 is performed by applying a fluorescent film raw material to at least one side of a substrate by a printing method, so that the in-plane film thickness distribution of the fluorescent film can be uniformly distributed. Sexual improvement. As a result, color unevenness can be suppressed, uniformity can be achieved, and performance can be stabilized.

The light-emitting device according to claim 8 or the light-emitting device according to claim 14 is performed by using a wavelength-converting member using an adhesive mainly composed of an inorganic material. Therefore, the light-emitting element produced from the semiconductor light-emitting wafer can be produced. Heat resistance is improved, and high output and high brightness can be achieved. In addition, since the wavelength conversion member is formed by coating the phosphor film material on at least one side of the substrate, the filling rate of the phosphor material in the phosphor film can be increased and the phosphor film can be thinned. The thickness of the phosphor film material includes a phosphor material and a binder material, and the binder material includes a silicon oxide precursor, a silicic acid compound, silica, and At least one of the group of crystalline silica. As a result, it is possible to reduce the size, improve the heat radiation efficiency, and increase the degree of freedom in design. In addition, since the phosphor film is obtained by reaction at normal temperature or heat treatment at a temperature of 500 ° C. or lower, it can be formed at a low temperature, and the deterioration of the characteristics of the phosphor material can be suppressed.

In addition, since it is performed in a manner in which a major component of the inorganic component is used as the main component of the adhesive, or at least a part of the inorganic bonded material is used, heat resistance can be further improved. In addition, since heat conductivity can be improved compared to resin, heat generated in the wavelength conversion member can be transferred to the semiconductor light emitting wafer side, and heat radiation can be improved through the semiconductor light emitting wafer. In addition, since the periphery of the light-emitting element can be sealed without using a resin, heat radiation can be further improved. This can suppress deterioration of the phosphor material.

In addition, if the average particle diameter of the primary particles of the phosphor material is set to 1 μm or more and 20 μm or less, or if If the film thickness distribution of the phosphor film is set to within ± 10%, or if the surface roughness of the phosphor film is set to 10 μm or less in arithmetic mean roughness Ra, , It can suppress color unevenness, uniformize, and stabilize performance. In addition, if the thickness of the substrate to be formed is set to 0.05 mm or more and 3 mm or less, the shape can be maintained and the size can be reduced.

The method for manufacturing a light-emitting device according to claim 15 is performed by applying a fluorescent film raw material to at least one side of a substrate by a printing method, so that the uniformity of the in-plane film thickness distribution of the fluorescent film can be improved. Sex. As a result, color unevenness can be suppressed, uniformity can be achieved, and performance can be stabilized.

10‧‧‧ Light-emitting device

11‧‧‧ substrate

12‧‧‧Semiconductor light emitting chip

13‧‧‧Reflector frame

14‧‧‧wavelength conversion component

14A‧‧‧forming substrate

14B‧‧‧Fluorescent Film

20‧‧‧Light-emitting element

21‧‧‧semiconductor light emitting chip

22‧‧‧ Adhesive

23‧‧‧wavelength conversion member

23A‧‧‧form substrate

23B‧‧‧Fluorescent Film

30‧‧‧light-emitting device

31‧‧‧ substrate

32‧‧‧ reflector box

FIG. 1 is a diagram showing a configuration of a light emitting device according to a first embodiment of the present invention.

Fig. 2 is a diagram showing a configuration of a light emitting element according to a second embodiment of the present invention.

FIG. 3 is a diagram showing a configuration of a light-emitting device using the light-emitting element of FIG. 2.

FIG. 4 is a characteristic diagram showing a change in luminance with time in an exposure test under a high temperature and high humidity environment of 85 ° C. and 85% RH.

Fig. 5 is a characteristic diagram showing changes in luminance with time in an exposure test under a dry and high-temperature environment at 150 ° C.

FIG. 6 is a characteristic diagram showing a change in luminance with time in an exposure test under a dry and high-temperature environment at 200 ° C.

FIG. 7 is a characteristic diagram showing the relationship between the exposure temperature and the luminous luminance after 24 hours in an exposure test in a dry high-temperature environment.

[Form of Implementing Invention]

Hereinafter, embodiments of the present invention will be described in detail with reference to the drawings.

(First Embodiment)

Fig. 1 is a diagram showing a structure of a light emitting device 10 according to a first embodiment of the present invention. This light-emitting device 10 is, for example, a plurality of semiconductor light-emitting wafers 12 made of LEDs mounted on a substrate 11. The semiconductor light emitting wafer 12 is, for example, one that emits ultraviolet light, blue light, or green light as excitation light. Among them, blue light is preferably emitted. This is because white can be easily obtained, and it has influences such as deterioration of surrounding members with respect to ultraviolet light, and the influence of blue light is small. Although the semiconductor light-emitting wafer 12 is, for example, not shown, electrical connections such as wirings and bumps formed on the substrate 11 can be used. A reflector frame 13 is formed around the semiconductor light-emitting wafer 12 so as to surround the whole, for example.

On the semiconductor light emitting wafer 12, for example, the wavelength conversion member 14 is disposed in contact with the semiconductor light emitting wafer 12. The wavelength conversion member 14 includes, for example, a base material 14A and a phosphor film 14B formed on at least one surface of the base material 14A. Although not shown, between each LED, that is, between the substrate 11 and the wavelength conversion member 14, an adhesive or a sealing member may be disposed to fill the space. The adhesive or the sealing member is preferably composed of an inorganic material and has high heat resistance. For example, the same adhesive as that used in the phosphor film 14B described below can be used. again The first figure shows, for example, a case where the wavelength conversion member 14 is arranged with the phosphor film 14B on the semiconductor light emitting wafer 12 side, but it may be performed in such a manner that the formation substrate 14A is arranged on the semiconductor light emitting wafer 12 side.

The formation of the substrate 14A is, for example, preferably made of glass, quartz, or sapphire that has translucency. In particular, if the sapphire structure is used, it is optically transparent like glass. It is even better than glass in that it can greatly improve the heat release property and suppress the deterioration of the phosphor material. The formation of the substrate 14A may be performed by using a high-purity polycrystalline alumina. This is because it is less expensive than sapphire, has less light absorption, and has the same thermal conductivity as sapphire. As a characteristic of forming the base material 14A, for example, it is preferable that the light transmittance is 90% or more in a wavelength region of 400 nm to 800 nm. In addition, when the base material 14A is formed, for example, when glass or sapphire is used, the surface may be roughened into a frosted glass shape in order to scatter light. In the case of using polycrystalline alumina, light is scattered due to the internal grain boundaries, so scattered light can be obtained without applying a special treatment to the surface.

The thickness of the base material 14A is, for example, preferably from 0.05 mm to 3 mm. This is because it can be miniaturized by setting it to 3 mm or less, and if it is thicker than 3 mm, it becomes thicker than necessary, and heat dissipation and light transmission properties are also reduced. This is because if it is thinner than 0.05 mm, it becomes difficult to maintain its own shape, and there is a possibility that the flatness cannot be maintained due to the influence of a fixing jig used during printing and the like. The formation of the substrate 14A and the formation of the phosphor film 14B may be performed by forming the wavelength conversion member 14 using a thickness of this type, or may be After the phosphor film 14B is formed using a thickness larger than this, the thickness of the substrate 14A to be formed is reduced by polishing or the like. However, in a case where the shape of the wavelength conversion member 14 is large and the formation substrate 14A itself has a task for holding the structure, the thickness of the formation substrate 14A may be thicker than 3 mm. In addition, the forming base material 14A may have any shape, a circular plate shape, or a quadrangular plate shape. In addition, although FIG. 1 shows a case of a flat shape, it may be a concave shape, a convex shape, or a light bulb shape.

The phosphor film 14B is, for example, a particulate phosphor material and a binder following the phosphor material, and may include a filler if necessary. The thickness of the phosphor film 14B is, for example, preferably from 30 μm to 1 mm, and more preferably from 50 μm to 500 μm. This is because if the thickness is too thin, the amount of phosphor material will decrease, and color adjustment will become difficult. If it is too thick, light scattering will increase too much, light absorption will become significant, and light will be difficult to export to the outside. The surface roughness of the phosphor film 14B (that is, the surface roughness of the surface of the phosphor film 14B opposite to the formation substrate 14A) is preferably 10 μm or less in terms of the arithmetic average roughness Ra. The film thickness distribution of the phosphor film 14B is preferably set within ± 10%. This is because it is possible to suppress color unevenness, uniformize, and stabilize performance. The surface roughness of the phosphor film 14B or the film thickness distribution of the phosphor film 14B can be adjusted by grinding or grinding after the phosphor film 14B is formed, for example.

The phosphor material system includes, for example, phosphor particles, and a coating layer may be formed on the surface of the phosphor particles. Examples of the phosphor particles include blue phosphors such as BaMgAl ₁₀ O ₁₇ : Eu, ZnS: Ag, Cl, BaAl ₂ S ₄ : Eu, or CaMgSi ₂ O ₆ : Eu, and Zn ₂ SiO _4. : Mn, (Y, Gd) BO ₃ : Tb, ZnS: Cu, Al, (M1) ₂ SiO ₄ : Eu, (M1) (M2) ₂ S: Eu, (M3) ₃ Al ₅ O ₁₂ : Ce, SiAlON: Eu, CaSiAlON: Eu, (M1) Si ₂ O ₂ N: Eu or (Ba, Sr, Mg) ₂ SiO ₄ : Yellow or green phosphors such as Eu, Mn, (M1) ₃ SiO ₅ : Eu or yellow, orange, or red phosphors such as (M1) S: Eu, (Y, Gd) BO ₃ : Eu, Y ₂ O ₂ S: Eu, (M1) ₂ Si ₅ N ₈ : Eu, ( M1) Red-based phosphors such as AlSiN ₃ : Eu or YPVO ₄ : Eu. In the above chemical formula, M1 includes at least one of a group including Ba, Ca, Sr, and Mg, M2 includes at least one of Ga and Al, and M3 includes at least one of a group including Y, Gd, Lu, and Te.

Wherein, considering the heat resistance of the wavelength converting member 14, preferably by the phosphor particles _{(M3) 3 Al 5 O 12} : Ce, SiAlON: Eu, CaSiAlON: Eu, (M1) Si 2 O 2 N: Eu , (M1) ₂ Si ₅ N ₈ : Eu, or (M1) AlSiN ₃ : Eu. M1 and M3 are as described above. The phosphor particles are selected in accordance with the type of the semiconductor light-emitting wafer 12 and the like. The phosphor material uses one kind or two or more kinds of phosphor particles. When plural kinds are used, they may be mixed and used, or they may be divided into a plurality of layers and laminated.

The coating layer system of the phosphor particles is preferably, for example, a composite oxide containing yttrium and aluminum including rare earth oxide, zirconia, titanium oxide, zinc oxide, aluminum oxide, yttrium-aluminum-garnet, magnesium oxide, And a metal oxide of at least one of the group of aluminum and magnesium composite oxides such as MgAl ₂ O ₄ as a main component. This is because the properties such as water resistance and ultraviolet light resistance can be improved. Among these, a rare earth oxide or zirconia is preferred. The rare earth oxide is more preferably one containing at least one element from the group consisting of yttrium, scandium, cerium, and lanthanum, and it is more preferable if zirconia is used. This is because a higher effect can be obtained or cost can be suppressed.

The average particle diameter of the primary particles of the phosphor material is, for example, preferably 1 μm or more and 20 μm or less. This is because by reducing the average particle diameter, it is possible to suppress color unevenness and uniformity. However, if the shrinkage is too small, the optical properties of the phosphor material itself are often lowered, and particles smaller than 1 μm may agglomerate twice and lose the effect of miniaturization. Therefore, it is preferably set to 1 μm or more.

The adhesive is obtained by reacting an adhesive raw material at a normal temperature or heat-treating at a temperature below 500 ° C. The adhesive raw material includes a silicon oxide precursor including a silicon oxide by hydrolysis or oxidation, and a silicic acid compound. , Silica, and amorphous silica. As the silicon oxide precursor, for example, those containing perhydropolysilazane, ethyl silicate, and methyl silicate as main components are preferably mentioned. This is because these silicon oxide precursors are easily converted into silicon oxide such as silicon dioxide by hydrolysis or oxidation under normal temperature or heat treatment, which can cause them to function as a binder. In addition, as a binder, it is not necessary for the silica precursor to react to completely become silica, and it may include an unreacted portion or an incompletely reacted portion.

Moreover, as a silicic acid compound, a sodium silicate is mentioned suitably, for example. The silicic acid compound may be used in a dehydrated state or a hydrate. As the silica or amorphous silica, for example, a nano-sized ultrafine particle powder is preferably used. For example, an ultrafine particle powder having an average particle diameter of 5 nm to 100 nm as a primary particle diameter is used. If 5 nm to 50 nm is used, The following ultrafine particles are more preferred. These silicic acid compounds, silica, or amorphous silica are dissolved or dispersed by The solvent can be solidified by heat treatment and drying, so that it can function as a binder.

The heat treatment temperature of the adhesive raw material is preferably set to 500 ° C or lower in order to reduce the thermal influence on the substrate 14A and the phosphor material. In the case of further reducing the thermal influence, the temperature is set to 300 ° C or lower. It is more preferable if the temperature is 200 ° C or lower. Moreover, it is preferable to perform it by making the adhesive raw material react at normal temperature, since there is no thermal influence. It is preferable to select the type of the binder raw material according to the heat resistance characteristics of the forming base material 14A and the phosphor material used, and adjust the binder raw material to react at normal temperature according to the adjustment, or heat-treat the binder raw material at a few degrees. In addition, when the gas environment during the heat treatment is easily oxidatively deteriorated due to heat, it is preferably a non-oxidizing gas environment such as a nitrogen atmosphere.

The filler is, for example, a material for adjusting the filling rate of the phosphor material, and is preferably composed of a translucent inorganic material, and examples thereof include silica particles, alumina particles, and zirconia particles. More preferably, it is a silicon oxide particle, and its form may be crystal or glass. The average particle diameter of the filler is preferably, for example, about 1 to 20 μm, which is the same as that of the phosphor material.

The wavelength conversion member 14 is formed by coating a phosphor film material containing a phosphor material and a binder material on at least one side of the formation substrate 14A, and reacting it at room temperature or heat treatment at a temperature of 500 ° C or lower. By. Examples of the coating method include a printing method, a spray method, a drawing method using a dispenser, and an inkjet method. Among them, if the printing method or the spray method is used, the phosphor film 14B can be improved. The uniformity of the in-plane film thickness distribution is better, and the most preferred is the printing method. The application may be repeated until the desired film thickness is obtained.

For example, if the printing method is used, one or two or more phosphor materials, a binder material, a diluent solvent, and a filler according to need are used to form a paste-like phosphor film material. On at least one side of the formation substrate 14A, coating is performed by a printing method (for example, screen printing). A printing method (for example, screen printing) is preferred because it can improve the uniformity of the in-plane film thickness distribution of the phosphor film 14B. For example, if the spray method is used, one or two or more phosphor materials, a binder material, a diluting solvent, and a filler as required are used to form a slurry phosphor. The film material is applied on at least one side of the formation substrate 14A together with a spray gas using a spray gun. It is preferable to uniformly move the spray diameter of the spray and the spray gun with a traverse at a constant speed.

After the phosphor base material is coated on the formation substrate 14A, the coated phosphor base material is dried to remove the diluent solvent, for example. At this time, if necessary, heating may be performed in a range of 500 ° C or lower, preferably 300 ° C or lower, and more preferably 200 ° C or lower. Thereby, the raw material of the adhesive is reacted at normal temperature or by heat treatment, or is solidified by heat treatment.

When the area of the phosphor film 14B is very small, a plurality of phosphor films 14B may be formed on the same surface of the substrate 14A and then cut by dicing or the like. get on. The phosphor film 14B may be formed on the entire surface of the substrate 14A, or may be patterned. If this is done once for the plurality of wavelength conversion members 14 Sexual treatment is preferable because cost reduction, time reduction, and efficiency can be achieved. In addition, even if a part of the phosphor film 14B has a variation in thickness, it can still be selected by slicing. Therefore, it is preferable to stabilize the quality. In addition, when a fine pattern is required, if it is screen printing, it is preferable because a large number of patterns can be printed on one substrate 14A at a time.

In this way, according to this embodiment, since the wavelength conversion member 14 is made by using an adhesive mainly composed of an inorganic material, the heat resistance to the heat generated from the semiconductor light emitting wafer 12 can be improved, and it is possible to achieve High output and high brightness. The wavelength conversion member 14 is formed by coating a phosphor film material on at least one side of the substrate 14A. The phosphor film material includes a phosphor material and a binder material, and the binder material is formed. Including at least one of the group consisting of a silicon oxide precursor, a silicic acid compound, silica, and an amorphous silica that becomes silicon oxide by hydrolysis or oxidation, the phosphor in the phosphor film 14B can be improved The filling rate of the material can reduce the thickness of the phosphor film 14B. As a result, it is possible to reduce the size, increase the heat radiation efficiency, and increase the degree of freedom in design. In addition, since the phosphor film 14B is obtained by reaction at normal temperature or heat treatment at a temperature of 500 ° C. or lower, it can be formed at a low temperature, and the deterioration of the characteristics of the phosphor material can be suppressed.

In addition, if the average particle diameter of the primary particles of the phosphor material is set to be 1 μm or more and 20 μm or less, or if the film thickness distribution of the phosphor film 14B is set to within ± 10%, If it is performed, or if the surface roughness of the phosphor film 14B is set to 10 μm or less in terms of the arithmetic mean roughness Ra, it can be suppressed. It can make the color uneven, uniformize and stabilize the performance.

In addition, if the base material 14A is formed by using sapphire or polycrystalline alumina, the heat conductivity is higher than that of glass, so that the heat release property can be improved, and the heat resistance temperature is also increased drastically, so that deterioration can be suppressed.

In addition, if the thickness of the formation base material 14A is set to 0.05 mm or more and 3 mm or less, the shape can be maintained and the size can be reduced.

Further, if the phosphor film material is applied by printing on at least one side of the substrate 14A, the uniformity of the in-plane film thickness distribution of the phosphor film 14B can be improved. As a result, color unevenness can be suppressed, uniformity can be achieved, and performance can be stabilized.

(Second Embodiment)

Fig. 2 is a diagram showing a configuration of a light emitting element 20 according to a second embodiment of the present invention. This light-emitting element 20 includes, for example, a semiconductor light-emitting wafer 21 and a wavelength conversion member 23, and the wavelength-conversion member 23 is disposed on the semiconductor light-emitting wafer 21 with an adhesive 22. The semiconductor light-emitting wafer 21 has, for example, a structure in which a plurality of semiconductor layers including a light-emitting layer are stacked, although not shown, and a pair of electrodes are arranged. Examples of the semiconductor light-emitting wafer 21 include LED wafers, and those that emit ultraviolet light, blue light, or green light are used as the excitation light. Among them, the semiconductor light emitting wafer 21 is preferably one that emits blue light. This is because white can be easily obtained, and it has influences such as deterioration of surrounding members with respect to ultraviolet light, and the influence of blue light is small. The semiconductor light-emitting wafer 21 may be a face-up type in which the light-emitting layer is arranged on the upper side, or it may be Face-down type with the light-emitting layer as the lower side.

The wavelength conversion member 23 is, for example, directly disposed on the light-emitting surface of the semiconductor light-emitting wafer 21 through the adhesive 22. The wavelength conversion member 23 includes, for example, a base material 23A and a phosphor film 23B formed on at least one surface of the base material 23A. In FIG. 2, the case where the phosphor film 23B is formed on one of the front surface and the rear surface of the base material 23A is shown. However, it may be performed on both surfaces, or it may replace the surface. It is performed on the side surface with the back surface, or on the side surface in addition to at least one of the front surface and the back surface. The wavelength conversion member 23 may be disposed with the formation substrate 23A on the semiconductor light emitting wafer 21 side, or may be disposed with the phosphor film 23B on the semiconductor light emitting wafer 21 side.

The configuration of the base material 23A and the phosphor film 23B is the same as that of the base material 14A and the phosphor film 14B described in the first embodiment. The wavelength conversion member 23 can be manufactured in the same manner as the wavelength conversion member 14 described in the first embodiment.

Adhesive 22 is obtained by reacting an adhesive raw material at a normal temperature or heat-treating at a temperature of 500 ° C or lower. The adhesive raw material includes a silicon oxide precursor including a silicon oxide by hydrolysis or oxidation, and a silicic acid compound. A phosphoric acid compound, and at least one selected from the group consisting of a silicone resin that has at least a part of its carbon detached by heating and becomes an inorganic bond. These materials are light-transmissive, and most of the main components are inorganic materials or at least a part of inorganic-bonded materials, so they have little effect on light-emitting characteristics, and are excellent in heat resistance.

As the silicon oxide precursor, for example, preferably, Perhydropolysilazane, ethyl silicate and methyl silicate are the main ingredients. These silicon oxide precursors are easily converted into silicon oxide such as silicon dioxide by hydrolysis or oxidation under normal temperature or heat treatment, and can cause them to function as the adhesive 22. Moreover, as the adhesive 22, it is not necessary that the silicon oxide precursor reacts completely to the silicon oxide, and it may include an unreacted portion or an incompletely reacted portion.

Preferred examples of the silicic acid compound include sodium silicate. The silicic acid compound may be used in a dehydrated state or a hydrate. Preferred examples of the phosphoric acid compound include aluminum phosphate. The silicic acid compound and the phosphoric acid compound can be solidified by dissolving or dispersing them in a solvent, heat-treating, and drying, so that they can function as an adhesive 22. Examples of silicone resins that become at least partially carbon-detached by heating and become inorganic bonds include organic polysiloxanes. Such a silicone resin has a high heat resistance because the organic group is detached by heating to remove organic groups, and it can also function as an adhesive 22.

The heat treatment temperature of the adhesive raw material is preferably set to 500 ° C or lower in order to reduce the thermal influence on the forming base material 23A and the phosphor material. In the case where it is necessary to further reduce the thermal influence, the temperature of 300 ° C or lower It is more preferable if the temperature is 200 ° C or lower. Moreover, it is preferable to perform it by making the adhesive raw material react at normal temperature, since there is no thermal influence. It is preferable to select the type of the adhesive raw material according to the heat resistance characteristics of the forming base material 23A and the phosphor material used, and adjust the adhesive raw material to react at normal temperature according to the adjustment, or heat-treat the adhesive raw material at a few degrees. In addition, the gas environment during heat treatment is in the phosphor material or semiconductor In the case where the bulk light emitting wafer 21 is susceptible to oxidative degradation due to heat, it is preferably set to a non-oxidizing gas environment such as a nitrogen environment.

In addition, when it is desired to form the adhesive 22 thickly, or when it is desired to increase the viscosity of the adhesive raw material, etc., a filler may be added to the adhesive raw material, and the adhesive 22 may include a filler. As the filler system, for example, it is preferable to be composed of a translucent inorganic material, and examples thereof include silica particles, alumina particles, and zirconia particles.

FIG. 3 shows a configuration example of a light emitting device 30 using the light emitting element 20. This light-emitting device 30 has a light-emitting element 20 mounted on a substrate 31. A reflector frame 32 is formed around the light emitting element 20, for example. The encapsulant may not be provided around the light emitting element 20. This is because the exothermic property can be improved as compared with the case of being covered with a resin encapsulant. Although not shown, it may be performed in such a manner that an encapsulant is disposed on the side of the light emitting element 20 to protect the circuit on the substrate 31. Although not shown, the encapsulant may be disposed so as to cover the upper surface of the light emitting element 20 as well. This is because the influence caused by direct contact with moisture or harmful gas from the outside can be reduced.

In this way, according to this embodiment, since the wavelength conversion member 23 uses an adhesive mainly composed of an inorganic material, the heat resistance to heat generated from the semiconductor light-emitting wafer 21 can be improved, and a high output and a high level can be achieved. Brightness. The wavelength conversion member 23 is formed by coating a phosphor film material on at least one side of the substrate 23A. The phosphor film material includes a phosphor material and an adhesive material, and the adhesive material includes Including oxidation by hydrolysis or oxidation At least one of the group of silicon oxide precursor, silicic acid compound, silica, and amorphous silica can increase the filling rate of the phosphor material in the phosphor film 23B, and can reduce the phosphor film. 23B thickness. As a result, it is possible to reduce the size, increase the heat radiation efficiency, and increase the degree of freedom in design. In addition, since the phosphor film 23B is obtained by reaction at normal temperature or heat treatment at a temperature of 500 ° C. or lower, it can be formed at a low temperature, and the deterioration of the characteristics of the phosphor material can be suppressed.

In addition, because the adhesive 22 is made of a semitransparent inorganic material having a major component or at least a part of an inorganic bonding material, heat resistance can be further improved. In addition, since heat conductivity can be improved compared to resin, heat generated in the wavelength conversion member 23 can be transferred to the semiconductor light emitting wafer 21 side, and heat radiation can be improved through the semiconductor light emitting wafer 21. In addition, since the periphery of the light-emitting element 20 can be sealed without the resin, the heat radiation performance can be further improved. This can suppress deterioration of the phosphor material.

In addition, if the average particle diameter of the primary particles of the phosphor material is 1 μm or more and 20 μm or less, or if the film thickness distribution of the phosphor film 23B is within ± 10%, or if If the surface roughness (calculated as the arithmetic average roughness Ra) of the phosphor film 23B is 10 μm or less, color unevenness can be suppressed, uniformity can be achieved, and performance can be stabilized.

In addition, if the substrate 23A is formed by using sapphire or polycrystalline alumina, the heat conductivity is higher than that of glass, so that the heat release property can be improved, and the heat resistance temperature can be increased drastically, so that deterioration can be suppressed.

In addition, if the thickness of the forming base material 23A is set as If it is performed in a range of 0.05 mm to 3 mm, the shape can be maintained and the size can be reduced.

[Example] (Examples 1-1 to 1-4)

First, a phosphor material, a binder material, a filler, and a diluent are mixed to prepare a phosphor film material. As the phosphor material, phosphor particles composed of Y ₃ Al ₅ O ₁₂ : Ce, and phosphor particles composed of CaAlSiN ₃ : Eu, each having an average particle diameter of about 15 μm, were used. As the raw materials of the binder, ethyl silicate was used in Example 1-1, perhydropolysilazane was used in Example 1-2, and sodium silicate hydrate was used in Example 1-3. 1-4 Use a solvent to suspend ultrafine particles of silica or amorphous silica. As the filler, silica particles having an average particle diameter of about 15 μm were used. As a dilution solvent, terpineol was used.

Next, the produced phosphor film raw material was printed on one side of the formation substrate 14A composed of a transparent glass plate having a thickness of 1 mm, and applied so as to have a desired thickness. Thereafter, the diluted solvent was removed by drying at 150 ° C. As a result, for each of the examples, a wavelength conversion member 14 having a phosphor film 14B having a thickness of about 80 μm formed on one side of the substrate 14A was obtained. When the surface roughness of the obtained phosphor film 14B was measured, the arithmetic mean roughness Ra was 10 μm or less. The film thickness distribution of the phosphor film 14B was also measured, and the result was within ± 10%. Using each of the obtained wavelength conversion members 14, a light-emitting device 10 as shown in FIG. 1 was produced. In the semiconductor light emitting wafer 12, a blue LED is used to produce a light emitting device 10 that emits white light.

The light-emitting device 10 of each example was energized, and as a result of a light-emitting test, good white light emission was obtained in any case. That is, it was found that even if the thickness of the phosphor film 14B is reduced, a good white color can be obtained and the size can be reduced.

(Examples 2-1 to 2-4)

First, in the same manner as in Examples 1-1 to 1-4, a phosphor material, a binder raw material, a filler, and a dilution solvent were mixed to prepare a phosphor film raw material. As the raw materials of the binder, ethyl silicate was used in Example 2-1, perhydropolysilazane was used in Example 2-2, and sodium silicate hydrate was used in Example 2-3, or, in Example 2-4 Use a solvent to suspend ultrafine particles of silica or amorphous silica. Next, a forming substrate 14A made of a transparent glass plate having a thickness of 1 mm and having a size capable of forming a plurality of wavelength conversion members 14 was prepared.

Then, one side of the substrate 14A was formed thereon, and the prepared phosphor film raw material was printed and applied so as to have a desired thickness. The diluted solvent was removed by drying at 150 ° C to form a plurality having a thickness of about 80 μm.份 phosphor film 14B. Thereafter, the formation substrate 14A on which the phosphor film 14B has been formed is cut into a plurality of pieces by dicing or the like to obtain each wavelength conversion member 14. Using each of the obtained wavelength conversion members 14, a light-emitting device 10 as shown in FIG. 1 was produced. In the semiconductor light emitting wafer 12, a blue LED is used to produce a light emitting device 10 that emits white light. The light-emitting device 10 of each example was energized, and as a result of a light-emitting test, good white light emission was obtained in any case.

(Examples 3-1 to 3-33, Comparative Examples 3-1 to 3-4)

First, mix phosphor materials, adhesive materials, and optionally dilute Release the solvent and the optional filler to make the phosphor film material. The material of the phosphor particles of the phosphor material in each example and each comparative example-the average particle diameter (particle diameter) of the phosphor particles-the amount of addition, the material of the filler-the average particle diameter (particle diameter)- The added amount and the material of the adhesive raw material-the added amount are shown in Tables 1 to 4. In addition, as the phosphor material, both or both of a phosphor material A and a phosphor material B are used. As the dilution solvent, α-terpineol was used.

Next, the prepared phosphor film material is coated on one side of the substrate 14A formed of a 100 mm square glass plate, and heat-treated or processed at room temperature to obtain a phosphor film 14B having a predetermined thickness. Wavelength conversion member 14. Using the obtained wavelength conversion members 14, light-emitting devices 10 as shown in FIG. 1 were prepared. The coating method of the phosphor film raw materials in each example and each comparative example, the heat treatment temperature, the average film thickness of the phosphor film 14B, the film thickness distribution of the phosphor film 14B, and the arithmetic of the phosphor film 14B The average roughness Ra is shown in Tables 2 and 4.

In addition, the film thickness measurement of the phosphor film 14B measures the thickness of the base material 14A beforehand, and measures the thickness of the wavelength conversion member 14 after the phosphor film 14B has been formed. The difference is taken as the film thickness. The average film thickness was measured for a total of 25 points in 5 columns and 5 rows with respect to a 100 mm square forming substrate 14A, and the average value of the film thickness was taken as the average film thickness. The film thickness distribution of the phosphor film 14B is calculated in accordance with the following calculation formula. The maximum film thickness is the maximum value among the measured 25-point film thickness, and the minimum film thickness is the minimum value among the measured 25-point film thickness.

Film thickness distribution (%) = ((maximum film thickness-minimum film thickness) / (maximum film thickness + minimum film thickness)) × 100

The arithmetic average roughness Ra of the phosphor film 14B is measured using a stylus-type surface roughness measuring device.

As shown in Tables 1 and 2, according to Examples 3-1 to 3-33 in which the average particle diameter of the phosphor particles and the filler is 20 μm or less, the film thickness distribution of the phosphor film 14B can be set to ± 10. Within%, the arithmetic mean roughness Ra is set to 10 μm or less.

Regarding the wavelength conversion member 14 produced in each Example and each comparative example, the initial light emission luminance as an initial characteristic was investigated. In addition, as a high-temperature and high-humidity test, an exposure test under a high-temperature and high-humidity environment at 85 ° C. and 85% RH was performed, and the reduction rate of luminous luminance after 2000 hours was investigated. In addition, as a dry high temperature test, an exposure test under a dry high temperature environment of 150 ° C or 200 ° C was performed, and the reduction rate of the luminous luminance after 2000 hours was investigated. The obtained results are shown in Tables 5 and 6. In Tables 5 and 6, the light emission luminance of the initial characteristics is a relative light emission luminance when the light emission luminance of Example 3-27 was set to 100. The luminous luminance reduction rate in the high-temperature and high-humidity test and the dry high-temperature test is the reduction rate from the luminous luminance of the initial characteristics in each example and each comparative example.

The results of Example 3-1 and Comparative Example 3-1 among the obtained results are shown in FIGS. 4 to 6. Figure 4 shows the results of an exposure test in a high-temperature, high-humidity environment at 85 ° C and 85% RH. Figure 5 shows the results at 150 ° C. The results of the exposure test in a dry high-temperature environment are shown in Figure 6. Figure 6 shows the results of the exposure test in a dry high-temperature environment at 200 ° C. In FIGS. 4 to 6, the relative luminance values in the case where the vertical axis represents the respective initial luminances of 100 are shown.

In addition, the wavelength conversion members 14 of Examples 3-1 to 3-4 and Comparative Example 3-1 were heated in an atmospheric oven, and subjected to a dry high-temperature environment exposure test at 100 ° C to 500 ° C to investigate changes in luminance with time. In addition, since there is a possibility that the wavelength conversion member 14 is damaged in a high temperature region exceeding 200 ° C., the visual appearance is also checked at the same time. The exposure time at each temperature was set to 24 hours. Among the obtained results, the results of Example 3-1 and Comparative Example 3-1 are shown in FIG. 7. In FIG. 7, the vertical axis represents a relative luminance value when each initial luminance is 100. Although not shown, the same results as in Example 3-1 were obtained for Examples 3-2 to 3-4.

As shown in Tables 5 and 6, according to this embodiment, the relative luminous luminance as an initial characteristic is 80% or more, but Comparative Examples 3-2 to 3-4 which have been heat-treated at 550 ° C or higher are as low as 70% or less.

In addition, as shown in Tables 5, 6, and 4 to 6, in Comparative Example 3-1 using a silicone resin, the reduction rate of the luminous luminance in the high-temperature and high-humidity test was 15%, and that in the high-temperature drying test at 150 ° C The luminous luminance reduction rate is 12%. In a dry high temperature test at 200 ° C., the wavelength conversion member is peeled off after 1200 hours, and the luminous luminance reduction rate after 33 hours is 33%. On the other hand, according to this embodiment, regardless of the high-temperature and high-humidity test, the high-temperature drying test at 150 ° C, and the high-temperature drying test at 200 ° C, the reduction rate of luminous luminance can be significantly improved to 7% or less.

In addition, as shown in FIG. 7, in Comparative Example 3-1 in which a silicone resin was used, the brightness maintenance rate decreased as the temperature became higher, and the phosphor film was powdered at 300 ° C or more due to chemical changes caused by heat. To peel. On the other hand, in Examples 3-1 to 3-4, there was no change in appearance, and no decrease in luminance maintenance rate was seen.

In addition, as shown in Tables 1, 2, and 5, the average particle diameter of the phosphor particles is larger than 20 μm, the thickness distribution of the phosphor film 14B is larger than ± 10%, and the arithmetic average roughness Ra ratio is larger. In Examples 3-34 to 3-36, which are larger than 10 μm, the average particle diameter of the phosphor particles and the filler is set as Examples 3-1 to 3-33 in which the thickness of the phosphor film 14B is set to within ± 10% and the arithmetic mean roughness Ra is set to 10 μm or less can improve the relative luminous intensity as an initial characteristic. .

(Examples 4-1, 4-2)

First, a phosphor material, a binder material, a filler, and a diluent are mixed to prepare a phosphor film material. The material of the phosphor particles of the phosphor material in each example-the average particle diameter (particle diameter) of the phosphor particles-the amount of addition, the material of the filler-the average particle diameter (particle diameter)-the amount of addition, adhesion Table 7 and 8 show the materials and added amounts of the agent raw materials. As the dilution solvent, α-terpineol was used. Next, on the side of the substrate 14A formed of a 100 mm square glass plate, the prepared phosphor film raw material is applied by a spray method or a brush, and heat-treated or processed at room temperature to obtain a predetermined thickness. The wavelength conversion member 14 of the phosphor film 14B. Using the obtained wavelength conversion members 14, light-emitting devices 10 as shown in FIG. 1 were prepared. The coating method, the heat treatment temperature, the average film thickness of the phosphor film 14B, the film thickness distribution of the phosphor film 14B, and the arithmetic average roughness Ra of the phosphor film 14B in each example Shown in Table 8. In addition, Tables 7 and 8 also show the values of Example 3-1.

As shown in Tables 7 and 8, compared with Example 3-1 applied by the printing method, the film thickness distribution of the phosphor film 14B in Examples 4-1 and 4-2 applied by the spray method or the brush was shown. And the arithmetic average roughness Ra becomes large, and the relative luminous luminance as an initial characteristic decreases. That is, it turns out that it is preferable to perform it by the method of apply | coating the phosphor film 14B by the printing method.

(Examples 5-1 to 5-4)

As the raw material of the adhesive, ethyl silicate (Example 5-1), aluminum phosphate (Example 5-2), and silicone resin (organic polysiloxane) which becomes at least a part of the carbon by heat removal are prepared. Alkane) (Example 5-3), sodium silicate (Example 5-4), an adhesive raw material was applied between two glass plates, and heat treatment was performed, whereby two glass plates were adhered with the adhesive 22. A liquid state is used for each adhesive raw material. In either embodiment, two glass plates can be bonded. Then, for each Example, the heat resistance test which heated from 100 degreeC to 300 degreeC was performed. The results are shown in Table 9. In Table 9, ○ indicates no peeling, and X indicates peeling.

As shown in Table 9, good heat resistance was obtained in any case. In particular, at least a part of the carbon of the aluminum phosphate of Example 5-2 and Example 5-3 was detached by heating to become an inorganic bond. Silicone resin and the sodium silicate of Example 5-4 were highly effective. That is, it can be seen that any of them is effective as the adhesive 22.

(Examples 6-1 to 6-4)

The heat resistance test was performed in the same manner as in Examples 5-1 to 5-4, except that the glass plate and the ceramic plate were bonded with the adhesive 22. Adhesive raw materials, Example 6-1 is ethyl silicate, Example 6-2 is aluminum phosphate, and Example 6-3 is a silicone resin (organic polymer) which becomes at least a part of carbon by heating to be detached. Siloxane), Example 6-4 is sodium silicate. The obtained results are shown in Table 10. In Table 10, ○ indicates no peeling, and X indicates peeling.

As shown in Table 10, both of them obtained good heat resistance. In particular, in Example 6-3, at least a part of the carbon was detached by heating to become an inorganic bonded silicone resin, and Example 6-6 4 sodium silicate is highly effective. That is, it can be seen that any of them is effective as the adhesive 22.

(Examples 7-1 to 7-4)

In addition to adding a filler of silica particles to the adhesive raw material, Other systems performed the heat resistance test in the same manner as in Examples 6-1 to 6-4. Regarding the raw materials of the adhesive, Example 7-1 is ethyl silicate, Example 7-2 is aluminum phosphate, and Example 7-3 is a silicone resin (organic-bonded) obtained by removing at least a part of carbon by heating (organic Polysiloxane), Example 7-4 is sodium silicate. The obtained results are shown in Table 11. In Table 11, ○ indicates no peeling, and X indicates peeling.

As shown in Table 11, the silicone resin of Example 7-3 in which at least a part of the carbon was detached by heating to become an inorganic bond, and the sodium silicate of Example 7-4 were highly effective. That is, it turns out that good adhesiveness can be obtained even if a filler is added.

(Production of the light-emitting devices of Examples 8-1 to 8-4)

First, a phosphor material, a binder material, a filler, and a diluent are mixed to prepare a phosphor film material. As the phosphor material, phosphor particles composed of Y ₃ Al ₅ O ₁₂ : Ce, and phosphor particles composed of CaAlSiN ₃ : Eu, each having an average particle diameter of about 15 μm, were used. As binder raw materials, ethyl silicate was used in Example 8-1, perhydropolysilazane was used in Example 8-2, sodium silicate hydrate was used in Example 8-3, or Example 8 -4 Suspended ultrafine particles of silica or amorphous silica with a solvent. As the filler, silica particles having an average particle diameter of about 15 μm were used. As a diluent, terpineol was used.

Next, the prepared phosphor film raw material was printed on one side of the forming substrate 23A made of a transparent glass plate having a thickness of 1 mm, and applied so as to have a desired thickness. Thereafter, the diluted solvent was removed by drying at 150 ° C. As a result, for each of the examples, a wavelength conversion member 23 having a phosphor film 23B having a thickness of about 80 μm formed on one side of the substrate 23A was obtained. The surface roughness of the obtained phosphor film 23B was measured. As a result, the arithmetic average roughness Ra was 10 μm or less. The film thickness distribution of the phosphor film 23B was also measured, and the result was within ± 10%.

Each of the obtained wavelength conversion members 23 and the separately prepared semiconductor light-emitting wafer 21 were adhered with an adhesive 22 to produce a light-emitting element 20 as shown in FIG. 2. As the adhesive raw materials, for each example, ethyl silicate, aluminum phosphate, silicone resin (organic polysiloxane), or sodium silicate, which becomes an inorganic bond by removing at least a part of carbon by heating, were used. After the bonding material is applied between the semiconductor light emitting wafer 21 and the wavelength conversion member 23, the bonding is performed by heating. The semiconductor light-emitting wafer 21 uses a blue LED wafer to produce a light-emitting element 20 that emits white light.

When the light-emitting element 20 of each example was energized and a light-emitting test was performed, it was found that good white light emission was obtained in any case.

As mentioned above, although this invention was demonstrated using embodiment, this invention is not limited to the said embodiment, Various deformation | transformation is possible. For example, although the structures of the light-emitting element 20 and the light-emitting devices 10 and 30 are specifically described in the above-mentioned embodiment, other structures may be used. Way of posing. In the above-mentioned embodiment, although the wavelength conversion members 14 and 23 are specifically described, other constituent elements may be separately provided.

In addition, in the first embodiment described above, the wavelength conversion members 14 and 23 of the phosphor films 14B and 23B including one or two or more phosphor materials are formed on at least one surface of the substrates 14A and 23A. In addition, instead of using a mixture of two types of phosphor materials, it is also possible to form the phosphor films 14B and 23B containing different phosphor materials by laminating at least one side of the substrates 14A and 23A. This may be performed by forming the phosphor films 14B and 23B containing different phosphor materials on both sides of the substrates 14A and 23A.

In addition, in the above-mentioned embodiment, although the semiconductor light-emitting wafers 12 and 21 are described in the case of using LEDs, it may be performed by using other semiconductor light-emitting wafers such as a laser light-emitting diode. In particular, according to the present invention, since high output can be achieved, it can be suitably used for applications requiring high output, such as laser projectors, LED headlights, or laser headlights.

[Industrial availability]

Can be used for light-emitting elements and light-emitting devices using semiconductor light-emitting wafers such as LEDs or laser light-emitting diodes.

Claims (8)

A light-emitting element is a light-emitting element in which a wavelength conversion member is disposed on a semiconductor light-emitting wafer by using an adhesive. The wavelength conversion member has a substrate and a phosphor film. The phosphor film is formed here. Either the front surface or the back surface of the forming substrate includes a particulate phosphor material and an adhesive. The wavelength conversion member uses the forming substrate as the semiconductor light emitting wafer side, and the forming substrate is directly formulated through the adhesive. The phosphor film is provided on the semiconductor light-emitting wafer, and the phosphor film is formed by coating a phosphor film material on one of a surface or a back surface of the substrate, and reacting the phosphor film at a normal temperature or a heat treatment at a temperature of 500 ° C or lower The phosphor film material includes the phosphor material and a binder material, and the binder material includes a silicon oxide precursor, a silicic acid compound, and an amorphous silica that become silicon oxide by hydrolysis or oxidation. At least one, the adhesive is obtained by reacting the adhesive raw material at normal temperature or heat-treating at a temperature of 500 ° C. or less, and the adhesive raw material includes oxidation by hydrolysis or oxidation. Precursor of silicon oxide, silicate compound, a phosphate compound, and by heating at least a portion of at least one carbon from the silicon becomes bonded in an inorganic resin. The light-emitting element according to claim 1, wherein the average particle diameter of the primary particles of the phosphor material is 1 μm or more and 20 μm or less. For example, the light-emitting element of claim 1, wherein the thickness distribution of the phosphor film is within ± 10%. The light-emitting element according to claim 1, wherein the surface roughness of the phosphor film is 10 μm or less based on the arithmetic average roughness Ra. The light-emitting element according to claim 1, wherein the forming substrate is made of glass, quartz, sapphire, or polycrystalline alumina. The light-emitting element according to claim 1, wherein the thickness of the forming substrate is from 0.05 mm to 3 mm. A light-emitting device is provided with a light-emitting element as claimed in claim 1. A method for manufacturing a light-emitting element, wherein the light-emitting element is provided on a semiconductor light-emitting wafer with an adhesive, and the wavelength-converting member has a phosphor formed on one of a surface or a back surface of the substrate. A phosphor film, the phosphor film comprising a particulate phosphor material and an adhesive; the manufacturing method is characterized in that the phosphor film is formed on a surface or a back surface of the substrate by using a printing method; It is formed by coating a phosphor film material and reacting it at normal temperature or heat treatment at a temperature below 500 ° C. The phosphor film material includes the phosphor material and a binder material, and the binder material includes a borrow material. At least one of a silicon oxide precursor, a silicic acid compound, and an amorphous silica that becomes silicon oxide by hydrolysis or oxidation. The semiconductor light emitting chip and the wavelength conversion member use the forming substrate as the semiconductor light emitting chip side, and The formation substrate and the semiconductor light-emitting wafer are directly adhered by an adhesive. The adhesive is reacted at a normal temperature or at a temperature of 500 ° C. or lower by using an adhesive raw material. It is obtained that the raw material of the adhesive includes at least one of a silicon oxide precursor, a silicic acid compound, and a phosphoric acid compound that become silicon oxide by hydrolysis or oxidation, and at least a portion of carbon that is detached by heating and becomes an inorganic bond. One.